Preparation of novel 5-acyloxy-4 (5H)-oxazolonium salts suited for use as intermediates for triazinone herbicides

ABSTRACT

Novel 5-acyloxy-4(5H)-oxazolonium salts of the formula ##STR1## in which R 1  represents an optionally substituted aliphatic group with up to 12 carbon atoms, an optionally substituted cycloalkyl group with 3 to 10 carbon atoms, an optionally substituted phenyl or naphthyl group or an optionally substituted heterocyclic group and 
     R 2  and R 3  are identical or different and represent a hydrogen atom or an optionally substituted aliphatic group with up to 8 carbon atoms or an optionally substituted phenyl group and 
     X.sup.⊖  represents the anion of an inorganic or organic acid having a pK a  value of less than 2, 
     are obtained in solution when an acyl cyanide of the general formula 
     
         R.sup.1 --CO--N                                            (II) 
    
     is reacted with a carboxylic acid anhydride of the general formula 
     
         R.sup.2 --CO--O--CO--R.sup.3                               (III) 
    
     wherein 
     R 1 , R 2  and R 3  each have the abovementioned meaning, in the presence of one or more inorganic or organic acids.

This is a continuation of application Ser. No. 828,932 filed Feb. 12,1986, now abandoned, which is a divisional of Ser. No. 360,495, filedMar. 22, 1982, now U.S. Pat. No. 4,594,427.

The invention relates to certain new 4(5H)-oxazolonium salts having anacyloxy radical in the 5-position, to an unobvious process for theirproduction and to their use as intermediates for the synthesis of known,herbicidally active 3,4,6-trisubstituted 1,2,4-triazin-5(4H)-ones.

4(5H)-Oxazolonium salts which carry hydrogen or lower alkyl groups inthe 5-position of the following formula are already known: ##STR2##wherein

R=lower alkyl;

R'=hydrogen or lower alkyl;

A=ClO₄, Cl or Br

These substances were prepared by reacting α-hydroxycarboxylic acidamides with anhydrides in the presence of 70% strength perchloric acid(Khim. Geterosikl. Soedin 1977, 702; Zh. Org. Khim. 12 (1976) 1134 andU.S.S.R. Patent No. 159,825 (25.1.1979)) or by reacting α-halogenoaceticacid bromides with amides (Ukr. chim. Z. 30 (1964) 3, 265), or byreacting chloroacetamides with acid chlorides (Ukr. Chim. Z. 30 (1964)6, 618 and ibid. 32 (1966) 2, 202).

Only 4(5H)-oxazolonium salts which carry hydrogen or alkyl groups in the5-position can be obtained according to any of the processes describedabove. 5-Acyloxy-4(5H)-oxazolonium salts are not producible by thesemethods.

The present invention now provides, as new compounds, the5-acyloxy-4(5H)-oxazolonium salts of the general formula ##STR3## inwhich

R¹ represents an optionally substituted aliphatic group with up to 12carbon atoms, an optionally substituted cycloalkyl group with 3 to 10carbon atoms, an optionally substituted phenyl or naphthyl group, or anoptionally substituted heterocyclic group and

R² and R³ are identical or different and represent a hydrogen atom or anoptionally substituted aliphatic group with up to 8 carbon atoms or anoptionally substituted phenyl group and

X.sup.⊖ represents the anion of an inorganic or organic acid having apK_(a) value of less than 2

According to the present invention we further provide a process for theproduction of a compound of the present invention characterized in thatan acyl cyanide of the general formula ##STR4## in which

R¹ has the abovementioned meaning, is reacted with a carboxylic acidanhydride of the general formula ##STR5## in which

R² and R³ are identical or different and have the abovementionedmeaning,

in the presence of one or more inorganic or organic acids having apK_(a) value of less than 2, and, if appropriate, in the presence of asolvent and, if appropriate, at a temperature between 0° and 120° C.

If pivaloyl cyanide and acetic anhydride are used as starting materialsand the reaction is carried out in the presence of concentratedsulphuric acid, the course of the reaction according to the presentinvention is illustrated by the following equation: ##STR6##

Preferred acyl cyanides of formula (II) to be employed as startingmaterials are those in which,

R¹ represents a straight-chain or branched alkyl group with 1 to 4carbon atoms optionally substituted by alkoxy with 1 to 4 carbon atoms,carbalkoxy with 1 to 4 carbon atoms in the alkoxy part, nitro, nitrileand/or halogen (such as fluorine, chlorine, bromine or iodine);represents a cycloalkyl group with 3 to 6 carbon atoms in the ringsystem which is optionally substituted by alkyl, alkoxy or carbalkoxy,each with up to 4 carbon atoms, nitro, nitrile and/or halogen (such asfluorine, chlorine and bromine), represents a phenyl or naphthyl groupwhich is optionally substituted by alkyl, alkoxy or carbalkoxy, eachwith up to 4 carbon atoms, nitro and/or halogen (such as, for example,fluorine, chlorine and bromine); or represents a 5-membered or6-membered heterocyclic group which contains 1 to 3 hetero-atoms (suchas oxygen, sulphur and/or nitrogen) in the ring, is furthermoreoptionally fused to a benzene ring, and is optionally substituted byalkyl, alkoxy or carbalkoxy, each with up to 4 carbon atoms, nitro,nitrile and/or halogen (such as fluorine, chlorine and bromine).

As examples of heterocyclic radicals which are suitable as radicals R¹there may in particular be mentioned morpholinyl, imidazolyl, pyrazolyl,pyrrolyl, isoxazolyl, piperidinyl, oxazolyl, 1,2,4-triazol-1-yl,1,2,4-triazol-4-yl, 1,2,3-triazolyl, 1,2,4-thiadiazol-2-yl,benzimidazolyl and furanyl.

Acyl cyanides of the formula (II) are known and can be preparedaccording to known processes (compare Angew. Chem. 68, pages 425-435(1965); also DE-OS (German Published Specification Nos.) 2,614,240,2,614,241, 2,614,242, 2,708,182 and 2,708,183).

Pivaloyl cyanide and benzoyl cyanide may be mentioned as acyl cyanidesof formula (II) which are particularly preferred for use in the processof the present invention.

Preferred carboxylic acid anhydrides of formula (III) also to beemployed as starting materials are those in which R² and R³independently represent an optionally chlorine-substituted alkyl groupwith 1 to 4 carbon atoms, or a phenyl group.

The carboxylic acid anhydrides of the formula (III) are, in some cases,available on an industrial scale and/or preparable in accordance withgenerally known methods, for example from the corresponding carboxylicacids. Where appropriate, the formation of the carboxylic acidanhydrides of the formula (III) can also be carried out in the reactionmedium, using anhydride-forming reagents (such as concentrated sulphuricacid).

Particularly preferred carboxylic acid anhydrides of formula (III), foruse in the process of the present invention, are acetic anhydride,propionic anhydride and the anhydrides of the chloroacetic acids.

The reaction according to the invention is carried out in the presenceof an acid having a pK_(a) value of less than 2. Suitable acids of thistype are inorganic acids, such as concentrated sulphuric acid, hydrogenhalide acids (for example anhydrous hydrogen chloride and hydrogenbromide), as well as perchloric acid and phosphoric acid. Furthersuitable acids are aliphatic and aromatic sulphonic acids and phosphonicacids as well as halogenoalkanecarboxylic acids (such as trifluoroaceticacid). Preferably, concentrated sulphuric acid is used.

It is possible to carry out the reaction according to the invention inthe presence of one or more such acids.

A particular preferred combination of reactants is pivaloyl cyanide asthe acyl cyanide of formula (II), acetic anhydride as the carboxylicacid anhydride of formula (III) and concentrated sulphuric acid as theacid.

The reaction temperatures can be varied within a substantial range. Ingeneral, the reaction is carried out, as stated above, at temperaturesbetween 0° and 120° C., preferably between about 10° and 60° C.

The reaction is in general carried out under normal pressure.

The reaction can be carried out in the absence or in the presence of asolvent or solubilizing agent. Suitable solubilizing agents are certainorganic solvents; glacial acetic acid and methylene chloride areparticularly suitable, as are dialkyl ethers (such as diethyl ether ordi-isopropyl ether).

In carrying out the process according to the invention, 0.5 to 10 mol,preferably 0.8 to 4 mol, of carboxylic acid anhydride of the formula(III) are in general employed per mol of acyl cyanide of the formula(II); a molar ratio of acyl cyanide of formula (II) to carboxylic acidanhydride of formula (III) of 1:1 to 1:2 is particularly preferred.

The acids required for carrying out the process according to theinvention are employed in amounts which range from catalytic quantitiesto more than stoichiometric quantities. In general, 0.5 to 10 mol,preferably 0.8 to 8 mol, particularly preferentially 1 to 4 mol, of acidare employed per mol of acyl cyanide of formula (II).

A molar ratio of carboxylic acid anhydride of formula (III) to acid of1:2 is particularly advantageous.

It follows that a molar ratio of acyl cyanide of formula (II) tocarboxylic acid anhydride of formula (III) to acid of 1:1:2 to 1:2:4 isvery particularly advantageous.

Advantageously, in carrying out the process, the procedure followed isto take the acid and the anhydride, or the mixture of carboxylic acidand anhydride-forming reagent, optionally with addition of a solvent,and to add the acyl cyanide, optionally in a solvent.

The reaction times are in general 1 to 10 hours.

The reaction mixture prepared in accordance with the process describedabove is a solution of the 5-acyloxy-4(5H)-oxazolonium salts of formula(I) according to the present invention.

The structure of the oxazolonium salts is shown clearly by the IR, ¹H-NMR and ¹³ C-NMR spectra of the reaction mixture. This may beillustrated using 5-acetoxy-5-tert.-butyl-2-methyl-4(5H)-oxazolonium ionof the salt of formula (Ia) as an example. The ion is obtained by mixingpivaloyl cyanide, acetic anhydride and anhydrous sulphuric acid in themolar ratio of 1:1:3, in accordance with the procedure described above.

The IR spectrum of this solution shows three strong signals in additionto the bands of the sulphuric acid.

These signals are allocated as follows (see Table 1), in accordance withthe comparable data of the known 4(5H)-oxazolonium perchlorates:

The signal at 1830 cm⁻¹ is due to the valency vibration of the carbonylgroup in the oxazolonium system. It is shifted to higher frequencies asa result of the vicinity of the positive fragment. The signal at 1785cm⁻¹ falls into the absorption range of ester carbonyl groups which areadjacent to electro-negative groups, as, for example, in enol esters. Itcan, in the present case, be allocated to the 5-acetoxy group. Thesignals between 1590 and 1530 cm⁻¹ can, in conformity with thecomparison substances, be allocated to the skeletal vibrations of theoxazolonium nucleus.

                                      TABLE 1                                     __________________________________________________________________________    IR spectra of the oxazolonium salts (ν in cm.sup.-1)                        Table 1                                                                                       ##STR7##                                                                                 ##STR8##                                                                                 ##STR9##                                                                              ##STR10##                                                                              Literature            __________________________________________________________________________     ##STR11##      1830       1783       --      1590  1570(Sh), 1530(Sh)                                                               --                      ##STR12##      1810       --         1720    1580, 1500                                                                             Zh. Org. Khim                                                                 12(1976) P. 1134        ##STR13##      1830       --         --      1590, 1548-1515                                                                        Khim. Geterosikl.                                                             Soedin 1977,           __________________________________________________________________________                                                           702                

The ¹ H-NMR spectrum of the solution containing the salt of formula (Ia)shows three signals (Table 2), which are in conformity with thestructure of the 4-(5H)-oxazolonium system.

                                      TABLE 2                                     __________________________________________________________________________    .sup.1 H-NMR spectrum of the 4(5H)-oxazolonium salts (δ in ppm)         against tetramethylsilane (TMS) as internal standard                                           Signals                                                                              (Allocation)                                                                             Solvent                                    __________________________________________________________________________     ##STR14##       1.30(3CH.sub.3)                                                                      2.85(CH.sub.3CO) 3.17(2-CH.sub.3)                                                        H.sub.2 SO.sub.4                            ##STR15##       1.40(2CH.sub.3)                                                                      2.30(CH.sub.3 CO) 3.08(2-CH.sub.3) 4.20(CH.sub.2)                             .52(5-CH)  CF.sub.3 COOH                              __________________________________________________________________________     (from Zh. Org. Khim. 12, (1976)1134)                                     

The signal at 1.30 ppm, with an integral corresponding to 9 protons, canundoubtedly be allocated to the three methyl groups of the tert.-butylgroup. The signal at 3.17 ppm corresponds to a methyl group next to astrongly positivated carbon atom. By comparison with the data in theliterature, this signal can be allocated to the 2-methyl group. Thesignal at 2.85 ppm must be allocated to the 5-acetoxy group. Compared tothe acetoxy group of the comparison substance, it is shifted by 0.55 ppmto a lower field. This is due to two effects:

The acetoxy group in the salt of formula (Ia) is bonded to a stronglypositivated carbon atom, as a result of which the signal of the CH₃group is shifted towards a lower field. Secondly, sulphuric acid,compared to trifluoroacetic acid as the solvent, causes an additionalshift to a lower field, through partial protonation of the estercarbonyl group.

An independent structural proof of the 5-acyloxy-4(5H)-oxazolonium ionspresent in the reaction mixture is provided by the ¹³ C-NMR spectra.Measurements were carried out on a reaction mixture of pivaloyl cyanide,acetic anhydride and sulphuric acid in a stoichiometric ratio of 1:2:4.

In addition to the two signals at 189 ppm and 19.5 ppm, which can beallocated to the protonated form of acetic acid, 8 further signals arefound (see Table 3), which can be allocated to the eight differentcarbon atoms of the 5-acetoxy-5-tert.-butyl-4(5H)-oxazolonium ion of thesalt of formula (Ia).

The signal at 193 ppm is due to a strongly positivated carbon atom,similar to the acetyl cation. This atom is the 2-C atom of theoxazolonium system. The signals at 171 ppm and 167 ppm can readily beallocated to the carbonyl carbon atoms of the 5-acetoxy group and to the4-C atom of the oxazolonium system. The signal at 109 ppm corresponds,in the shift position, to a carbon atom between two oxygen atoms, as inketals, and is, in the present case, allocated to the 5-C atom of theoxazolonium system. The signal at 39.1 ppm corresponds to the tertiarycarbon atom and the signal at 22.7 ppm to the primary carbon atoms ofthe tert.-butyl group. The signals at 20.6 ppm and 17.0 ppm are due tothe carbon atoms of the methyl groups on C-2 of the oxazolonium systemand in the acetyl group.

    TABLE 3      .sup.13 C-NMR spectra (δ in ppm) Allocation             Substance S     olvent      ##STR16##      ##STR17##      ##STR18##      ##STR19##      ##STR20##      ##STR21##      ##STR22##      tertiaryC      ##STR23##      ##STR24##      ##STR25##      D.sub.2 SO.sub.4 189         19.5      ##STR26##      ##STR27##      CDCl.sub.3   182   112  45 24.5      ##STR28##      D.sub.2      SO.sub.4  193  171 167  109 39.1 22.7 20.617.0

The 5-acyloxy-4(5H)-oxazolonium salts of formula (I) which can beprepared by the process according to the invention are novel and can beused as intermediates for the preparation of known herbicidally activetriazinones (compare, for example, German Patent Nos. 1,542,873 and1,795,784).

According to the present invention we thus further provide a process forthe production of a 1,2,4-triazin-5(4H)-one of the general formula##STR29## in which

R¹ has the abovementioned meaning,

R⁴ represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms,an aryl group with 6 to 10 carbon atoms or an amino or mono ordisubstituted amino group and

R⁵ represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms,an aryl group with 6 to 10 carbon atoms, a hydroxyl group, an alkoxygroup with 1 to 4 carbon atoms, an aryloxy group with 6 to 10 carbonatoms, a mercapto group, an alkylmercapto group with 1 to 4 carbon atomsor an amino or mono- or di-substituted amino group,

characterized in that a 5-acyloxy-4(5H)-oxazolonium salt of formula (I),in solution, is reacted, either directly or after prior hydrolysis tothe α-ketocarboxylic acid N-acylamide of the general formula

    R.sup.1 --CO--CO--NH--CO--R.sup.3                          (V)

in which

R¹ and R³ have the abovementioned meanings, with a hydrazine derivativeof the general formula ##STR30## in which

R⁴ and R⁵ have the abovementioned meaning.

The process according to the present invention for the production of acompound of formula (IV) can be carried out with good yields.

The 5-acyloxy-4(5H)-oxazolonium salts of formula (I) according to theinvention are accordingly a novel, valuable class of intermediates, forexample for the synthesis of α-ketocarboxylic acid N-acylamides (and -by further hydrolysis - of the corresponding α-ketocarboxylic acids ofthe formula R¹ --CO--COOH, which have diverse uses) and of herbicidallyactive 1,2,4-triazin-5-one derivatives.

The α-ketocarboxylic acid N-acylamides of formula (V) as such are thesubject of U.S. application Ser. No. 235,497, filed Feb. 19, 1981, nowpending.

The reaction of these α-ketocarboxylic acid N-acylamides of formula (V)with thiocarbohydrazide (a compound of formula (VI) with R⁴ =NH₂ and R⁵=SH) to give triazinones (compounds of formula (IV) with R⁵ =SH) is alsoa subject of an earlier patent application, Ser. No. 235,495, filed Feb.19, 1981, now pending.

Within the framework of the present invention, the direct reaction ofthe novel 5-acyloxy-4(5H)-oxazolonium salts of formula (I) with thehydrazine derivatives of formula (VI) to give the desired1,2,4-triazin-5(4H)-one derivatives of formula (IV) is preferred overthe process variant which involves the prior hydrolysis of the salts offormula (I) and intermediate isolation of the α-ketocarboxylic acidN-acylamides of formula (V).

The process described here, proceeding via the novel5-acyloxy-4(5H)-oxazolonium salts according to the invention, for thepreparation of herbicidally active asymmetrical triazinones of formula(IV) is technically superior to the comparable previously known processproceeding via α-ketocarboxylic acid N-tert.-butylamides (see U.S. Pat.Nos. 4,175,188 and 4,224,226).

In particular, the 5-acyloxy-4(5H)-oxazolonium salts of formula (I)according to the invention can be cyclised almost quantitatively, undervery mild conditions, with hydrazine derivatives of formula (VI), forexample thiocarbohydrazide or S-methyl-thiocarbohydrazide, to giveasymmetrical triazinones, which are obtained directly in high purity,whereas the previously known α-ketocarboxylic acid N-tert.-butylamidesmust, for this purpose, be heated with thiocarbohydrazide for severalhours at 100° C., and give yields of only about 70%.

In carrying out the process for the preparation of triazinones from thesalts of formula (I) according to the invention, 1 to 1.5 mol of ahydrazine derivative of the formula (VI) are in general employed per molof a salt of the formula (I). The reaction temperatures are in generalbetween 0° and 100° C., preferably between 15° and 60° C.

For example, the 5-acetoxy-5-tert.-butyl-2-methyl-oxazolonium salt offormula (Ia) gives the herbicidally particularly active compound4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5(4H)-one of formula(IVb) (compare German Patent Specification No. 1,795,784) in accordancewith the following equations: ##STR31##

The methylation (IVa)→(IVb) is already known (compare, for example,Chem. Ber. 97, pages 2173-8 (1964); (see U.S. Pat. No. 4,175,188).

The preparative examples which follow illustrate the invention further.

PREPARATIVE EXAMPLES Example 1 ##STR32##

25.6 g (0.25 mol) of acetic anhydride followed by 27.8 g (0.25 mol) ofpivaloyl cyanide were introduced, in each case at room temperature, into49.0 g (0.5 mol) of concentrated sulphuric acid. After a further 4hours' stirring, spectroscopic measurements were carried out on thereaction mixture. The characteristic bands of the IR spectrum are shownin Table 1, the signals of the ¹ H-NMR spectrum in Table 2 and thesignals of the ¹³ C-NMR spectrum in Table 3.

Example 2

    (CH.sub.3).sub.3 C--CO--CO--NH--CO--CH.sub.3               (Va)

25.6 g (0.25 mol) of acetic anhydride, followed by 27.8 g (0.25 mol) ofpivaloyl cyanide, were introduced, in each case at room temperature,into 49.0 g (0.5 mol) of concentrated sulphuric acid. After a further 4hours' stirring, 150 g of ice water were added to the reaction mixtureand the batch was stirred thoroughly. The reaction product whichprecipitated was filtered off, washed with 100 ml of water and dried.37.0 g (86% of theory) of trimethylpyruvic acid N-acetylamide wereobtained as colorless glistening flakes of melting point 82° to 84° C.;purity, according to gas-chromatographic determination,>98%.

Example 3 ##STR33##

A solution of 5-t-butyl-5-acetoxy-2-methyl-4(5H)-oxazolonium hydrogensulphate was prepared analogously to Example 1. This solution was thenadded dropwise to a suspension of 29.3 g (0.275 mol) ofthiocarbohydrazide in 300 ml of water, and thereafter the mixture wasstirred for one hour at 50° C. It was cooled and the precipitate whichhad separated out was filtered off and washed until neutral. Afterdrying, 48.0 g (95.9% of theory) of4-amino-6-t-butyl-3-mercapto-1,2,4-triazin-5(4H)-one were obtained,melting point 212° to 215° C.

Example 4 ##STR34##

A solution of the oxazolonium hydrogen sulphate of formula (Ia) wasprepared analogously to Example 1. This solution was added dropwise to asuspension of 74.4 g (0.3 mol) of S-methylthiocarbohydrazide hydriodidein 300 ml of water and the mixture was then stirred for 0.5 hour at 50°C. An oil separated out, and this was separated off and stirred twicewith 100 ml of water. 39.9 g (74.6% of theory) of crude4-amino-6-t-butyl-3-methylmercapto-1,2,4-triazin-5(4H)-one wereobtained. A recrystallized sample melted at 121° to 123° C.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A process for the preparation of an acidicsolution of a 5-acyloxy-4(5H)-oxazoloniumn salt of the formula ##STR35##in which R¹ represents a straight-chain or branched alkyl group with 1to 4 carbon atoms optionally substituted by alkoxy with 1 to 4 carbonatoms, carbalkoxy with 1 to 4 carbon atoms in the alkoxy part nitro,nitrile and/or halogen; represents a cycloalkyl group with 3 to 6 carbonatoms in the ring system which is optionally substituted by alkyl,alkoxy or carbalkoxy, each with up to 4 carbon atoms, nitro, nitrileand/or halogen; represents a phenyl or naphthyl group which isoptionally substituted by alkyl, alkoxy or each with up to 4 carbonatoms, nitro and/or halogen or represents a morphoinyl, imidazolyl,pyrazolyl, pyrrolyl, isoxazolyl, piperidinyl, oxazolyl,1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, 1,2,3-triazolyl,1,2,4-thiadiazol-2-yl, benzimindazolyl or furanyl which is optionallysubstituted by alkyl, alkoxy or carbalkoxy, each with up to 4 carbonatoms, nitro, nitrile and/or halogen;R² and R³ represent an optionallychlorine-substituted alkyl group with 1 to 4 carbon atoms or a phenylgroup, and X represents the anion of an inorganic or organic acid havinga pK_(a) value of less than about 2 (1) said process consistingessentially of reacting an acyl cyanide of the formula ##STR36## with acarboxylic acid anhydride of the formula ##STR37## in the presence of atleast one inorganic or organic acid having a pK_(a) value of less thanabout 2 and (2) forming an acidic solution of5-acyloxy-4(5H)-oxazolonium salt.
 2. A process according to claim 1,wherein the reaction is carried out at a temperature between 0° and 120°C.
 3. A process according to claim 1, wherein the reaction is carriedout in the presence of a solvent.
 4. A process according to claim 1,wherein the acyl cyanide and carboxylic acid anhydride are employed in amolar ratio of about 1:0.5 to 1:10.
 5. A process according to claim 1,wherein the acyl cyanide and acid are employed in a molar ratio of about1:0.5 to 1:10.
 6. A process according to claim 1, wherein the carboxylicacid anhydride and acid are employed in a molar ratio of about 1:2.
 7. Aprocess according to claim 1, wherein the acyl cyanide, carboxylic acidanhydride and acid are employed in the molar ratio of about 1:1:2 to1:2:4.
 8. A process according to claim 1, wherein pivaloyl cyanide isemployed as the acyl cyanide, acetic anhydride as the carboxylic acidanhydride and concentrated sulphuric acid as the acid.
 9. A processaccording to claim 8, wherein the reaction is carried out at atemperature between about 10° and 60° C. in the presence of a solvent,and the acyl cyanide, carboxylic acid anhydride and acid are employed inthe molar ratio of about 1:1:2 to 1:2:4.
 10. A process according toclaim 1, wherein the reaction is carried out at a temperature between10° and 60° C.
 11. A process according to claim 1, wherein the reactionis carried out in the absence of a solvent.